Methods for fabrication of silica aerogels with custom shapes using freeze drying

ABSTRACT

A method of synthesizing aerogels and cross-linked aerogels are described that incorporate freeze-drying in lieu of supercritical solvent drying. Advantages over supercritical drying include a reduction in hazard risks posed by drying at supercritical conditions as well as the ability to up-scale the process to accommodate large pieces of material without introducing risk. In addition, inexpensive and more sophisticated mold technologies, which are not impervious to supercritical conditions, can be used to produce aerogel materials according to the freeze-drying method of the invention. This introduces a level of freedom never before available for the production of aerogel components.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application relies on the disclosure of and claims priorityto and the benefit of the filing date of U.S. Provisional ApplicationNo. 62/325,525, filed Apr. 21, 2016 and is a Continuation-In-Partapplication of U.S. patent application Ser. No. 15/500,376 filed Jan.30, 2017, which is a national stage application of InternationalApplication No. PCT/US2015/043234, filed Jul. 31, 2015 and published asInternational Publication No. WO 2016019308 on Feb. 4, 2016, which PCTrelies on the disclosure of and claims priority to and the benefit ofthe filing date of U.S. Provisional Application No. 62/031,211, filedJul. 31, 2014. The disclosures of each of these applications are herebyincorporated by reference herein in their entireties.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to the field of aerogel syntheticchemistry and processing. More particularly, the present invention inembodiments relates to fabrication of native and cross-linked aerogelsin monolithic form by freeze-drying wet gels.

Description of Related Art

Aerogels are solid materials of extremely low density, produced byremoving the liquid component from a conventional wet gel. They areultra-light, highly porous and highly thermally insulating materialscomposed of a network of interconnected nanostructures. Their typicaldensity is lower than 0.1 g/cm³, their surface area is in the 700-1000m²/g range and their thermal conductivity can be as low as 2.1 mW/mK(see N. Leventis, Accounts of Chemical Research., 2007, 40, 874(“Leventis, 2007”) and A. C. Pierre, G. M. Pajonk, Chem. Rev., 2002,102, 4243 (“Pierre, 2002”)). Because of this unique combination ofproperties, aerogels are being considered for applications as varied asthermal and sound insulation for the aerospace industry, as absorbentsfor environmental remediation and as catalyst supports. However,aerogels are also mechanically fragile and their use has been limited toniche applications such as thermal insulation for the Mars Rovers, ascollectors of space and comet dust and as Cerenkov detectors (seeLeventis, 2007 and Pierre, 2002). By way of background, other efforts inthis area include those described by Leventis et al., such as in U.S.Pat. Nos. 7,732,496 and 8,227,363 as well as in U.S. Patent ApplicationNo. 2011/0250428 A1, hereby incorporated by reference in theirentireties.

Aerogels are fabricated starting from wet gels. Wet gels are porousmaterials with the same porosity and surface area of aerogels. However,the pores of wet gels are filled with solvent and precursors used forthe synthesis. Typically, the solvent is some alcohol (e.g., methanol,ethanol, or propanol) and some water is added to catalyze the syntheticreaction. The solvent typically cannot be evaporated without crackingthe gel because of capillary forces. That is, the solvent adheresstrongly to the pore walls and induces cracks and pore collapse when itevaporates. To prevent cracking, a fluid with a low (ideally zero)surface tension is employed, which minimizes the capillary forces. Thissolvent is typically a supercritical solvent. Supercritical solventdrying has been described in detail in the inventors' previous work (seeInternational Patent Application Publication No. WO 2016019308, which ishereby incorporated by reference in its entirety). While this previousmethod was a significant step forward in one-step processing of aerogelmaterials, supercritical solvent drying becomes increasingly hazardouswhen up-scaled and limits the variety of mold technologies viable forproduction of materials with custom shapes since most mold materials areaffected by supercritical conditions and/or supercritical solvents.Given these limitations, there is a need in the art for improvedprocesses for producing aerogels.

SUMMARY OF THE INVENTION

Embodiments of the present invention provide methods for the productionof both native silica and cross-linked aerogel monoliths thatincorporate freeze-drying in lieu of supercritical solvent drying.According to embodiments of the methods of the invention, the solventwithin the wet gel is frozen. The gel monolith is then placed in avacuum chamber where the solvent is removed by sublimation. Advantagesover supercritical drying, only some of which are discussed herein,include a reduction in hazard risks posed by drying at supercriticalconditions as well as the ability to up-scale the process to accommodatelarge pieces of material without introducing risk. A second advantage ofthe invention is a substantial reduction in capital expenditures.Autoclaves used for supercritical drying require thick walls and poseliability issues because of the high pressures (on the order of 70atmospheres) used in supercritical drying. Freeze drying uses vacuumchamber(s) instead which are much cheaper to produce and pose minimalliability issues. Typically, a supercritical drying autoclave costs 10times more than a freeze drying vacuum chamber of the same capacity. Inaddition, inexpensive and more sophisticated mold technologies, whichare not impervious to supercritical conditions, can be used to produceaerogel materials according to the freeze-drying method of theinvention. This introduces a level of freedom never before available forthe production of aerogel components.

According to one embodiment, the present invention provides a method forproducing an aerogel which includes providing a first solutioncomprising an alkoxide, providing a second solution comprising acatalyst, mixing the first and second solutions to provide a gelationmixture or composition, and optionally pouring the solutions into amold. The mixing of the first and second solutions results in formationof a wet gel as a result of hydrolysis of the alkoxide andpolymerization of the hydrolyzed alkoxide. After gelation, the wet gelis dried to form an aerogel. According to embodiments, the gel is driedby freeze-drying.

According to another embodiment, the present invention provides a methodfor producing an aerogel which includes mixing a first solutioncomprising an alkoxide, a photoinitiator, and a first acrylic monomerand a second solution comprising a catalyst and a second acrylic monomerand optionally pouring the solutions into a mold. The mixing stepresults in the formation of a wet gel as a result of hydrolysis of thealkoxide and polymerization of the hydrolyzed alkoxide. The methodfurther includes exposing the wet gel to a source of visible light withsufficient intensity to catalyze cross-linking of the wet gel, anddrying the wet gel. According to embodiments, the gel is dried by freezedrying.

According to another embodiment, the present invention provides a methodfor producing an aerogel which includes mixing an alkoxide and acatalyst together in an aqueous solution to provide a composition andoptionally pouring the composition into a mold. The mixing of alkoxideand catalyst together results in formation of a wet gel as a result ofhydrolysis of the alkoxide and polymerization of the hydrolyzedalkoxide. After gelation, the method further includes performing asolvent exchange step to remove water from the wet gel, andfreeze-drying the wet gel to remove solvent from the wet gel to form anaerogel.

According to another embodiment, the present invention provides a methodfor producing an aerogel which includes mixing an alkoxide, a catalyst,an acrylic monomer, a silica derivatizer and a polymerization initiatortogether to provide a composition, and optionally pouring thecomposition into a mold. The mixing step results in the formation of awet gel as a result of hydrolysis of the alkoxide and polymerization ofthe hydrolyzed alkoxide. The method further includes exposing the wetgel to a stimulus with sufficient intensity to catalyze cross-linking ofthe wet gel by the polymerization initiator, and freeze-drying thecross-linked wet gel to form an aerogel.

According to another embodiment, the present invention provides methodsof improving the transparency of aerogels through mechanisms such asaltering pore size and pore size distribution, changing the size and/orshape of skeletal aggregates, or removing light-scattering reagents.

These embodiments and additional embodiments of the invention and theirdetails will be provided in the foregoing Detailed Description.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings illustrate certain aspects of embodiments ofthe present invention, and should not be used to limit the invention.Together with the written description the drawings serve to explaincertain principles of the invention.

FIG. 1A is a photograph showing a side view of a cross-linked silicaaerogel fabricated by freeze drying.

FIG. 1B is a photograph showing a top view of an aerogel fabricated byfreeze drying, where gelation byproducts such as methanol were partiallyremoved by evaporation prior to freezing and where the dried monolith isilluminated from below to show improved optical characteristics.

FIG. 1C is an image showing an aerogel sample fabricated as in FIG. 1A,after heating to 400° C., showing that removal of the cross-linkingpolymer improves transparency.

FIG. 1D is an image of a native aerogel patterned with a polymerhoneycomb and compressed uniaxially, where areas between the polymerhoneycomb have become transparent and where all samples were reinforcedby acrylic polymers which yield opaque aerogels.

FIGS. 2A and 2B are images of exemplary comparison aerogels prepared byway of supercritical drying, with FIG. 2A showing a silica aerogelcylinder (0.25 inch diameter, UCS=4 MPa) and FIG. 2B showing an aerogelcrosslinked with polyurethane in disk form (0.25 inch thick, UCS=186MPa).

FIGS. 3A and 3B are graphs showing simulations of light scattering fromaggregates of silica nanoparticles with different shapes. N indicatesthe number of silica nanoparticles in the aggregate. Note how thescattering lobe (and thus haze) is wider for the globular aggregate(FIG. 3B) than for the fractal aggregate (FIG. 3A). N indicates thenumber of nanoparticles in the aggregate. Adapted from T. Kozasa, J.Blum, T. Mukai, “Optical properties of dust aggregates I.”, Astron.Astrophys. 263, 423-32 (1992) and T. Kozasa, J. Blum, T. Mukai, “Opticalproperties of dust aggregates II,” Astron. Astrophys. 276, 278-88(1993).

FIG. 4 is a diagram showing an example of cross-linking of silicaaerogels. The gelation solution contains a monomer which engages themoiety at the surface of silica nanoparticles when polymerization isinitiated.

FIG. 5 is an image of a series of aerogels cross-linked withpolyurethane at a temperature of 100° C. The cross-linker concentrationincreases from left (native aerogels) to right, and the transparency ofthe materials with the lowest cross-linker concentration resembles thatof native aerogels. All samples had a diameter of 7 mm. Adapted from N.Leventis, C. Sotiriou-Leventis, G. Zhang, and A.-M. M. Rawashdeh NanoLetters, 2002, 2 (9), pp 957-960.

FIGS. 6A and 6B are schematic diagrams showing the effect of conformalcoating (orange) on different skeletal morphologies (white) with FIG. 6Ashowing a fibrillar skeletal morphology. The conformal coating increasesaggregate size by approximately twice the coating's thickness. FIG. 6Bshows a Globular skeletal morphology. The conformal coating fills thegaps between the particles and gives rise to a large aggregate.

FIG. 7 is an image of a transparent aerogel produced by freeze drying.The aerogel had been strengthened by prolonged aging, and a DCCA wasused to control pore size distribution. Adapted from E. Degn Egeberg, J.Engell, “Freeze drying of silica gels prepared from siliciumethoxid”,Journal de Physique Colloques, 1989, 50 (C4), p. C4-23-C4-28.

FIGS. 8A-8C are images of flexible aerogels with FIG. 8A showing thetransparency of different formulations and FIG. 8B showing demonstrationof stress recovery. Adapted from K. Kanamori, M. Aizawa, K. Nakanishi,and T. Hanada, “New Transparent Methylsilsesquioxane Aerogels andXerogels with Improved Mechanical Properties”, Adv. Mater. 2007, 19,1589-1593. FIG. 8C shows flexible aerogel fabricated by the inventors byfreeze drying using the precursor formulation reported in Kanamori etal.

FIG. 9 is a graph showing simulation of the U value of a glass panecoated with a coating of emissivity 0.1, attached to an aerogel panewith thermal conductivity of 30 mW/m-K. The total thickness of theretrofit is kept to ¼ inch.

FIGS. 10A-B are photographs of aerogel samples prepared according toembodiments described in this disclosure. FIG. 10A shows a transparentsample with a thickness of 6 mm, while FIG. 10B shows a translucent 3 mmdisk prepared without an oven aging step.

FIG. 11A-B are graphs showing pore size distributions calculated usingthe BJH approximation (FIG. 11A) and providing an adsorption isotherm oftransparent and translucent regions of the same sample (FIG. 11B), wherethe translucent region was in the core and had been frozen more slowlythan the outer regions.

DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS OF THE INVENTION

Reference will now be made in detail to various exemplary embodiments ofthe invention. It is to be understood that the following discussion ofexemplary embodiments is not intended as a limitation on the invention.Rather, the following discussion is provided to give the reader a moredetailed understanding of certain aspects and features of the invention.

In embodiments, the present invention provides a method of fabricationof native and cross-linked silica aerogels in monolithic form byfreeze-drying. The silica aerogels may be fabricated into a variety ofcustom shapes. The custom aerogel shapes may be used in a variety ofthermal insulation applications or as window panes.

According to embodiments, the processes used for native and cross-linkedaerogels differ in one main aspect. For native silica aerogels, thesynthesis is carried out using mostly water as the solvent for gelation.This water must be removed by solvent exchange. For cross-linkedaerogels, the inventors prepared a composition (which may also bereferred to as a gelation solution, gelation mixture, a mixture, or asolution) with a very limited amount of solvent, e.g., water (about 4%by volume of solvent). This small amount of water was sufficient toinduce gelation, but it did not induce cracks into freeze driedmonoliths. For this technique, the wet gel is freeze dried starting fromthe parent solution. That is, there is a single synthetic step and nosolvent exchanges are necessary, although if desired solvent exchange(s)can be performed. The key to the success of this method, used for thesynthesis of cross-linked aerogels, is that the silica backbone iscross-linked with a conformal polymer coating which lends the rigidbackbone some flexibility during freezing of the solvent.

According to embodiments (as detailed in the foregoing Example),freeze-dried native silica aerogels have been obtained with a surfacearea of ˜400 m²/g. Using the inventors' one-pot freeze-drying technique,cross-linked silica aerogels have been obtained with a surface area of˜100 m²/g and a modulus of 50 MPa. All these values are in line withthose of native and cross-linked aerogels fabricated by supercriticaldrying.

The aerogels may be produced in molds having a variety of shapessuitable for thermal insulation and/or window applications, or may beproduced without using a mold. As the aerogels may be manufactured asmonoliths with a volume of up to 100 cm³, the gels may be cast into avariety of shapes suitable for a variety of applications.

Fabrication of Native Silica Aerogels

According to embodiments, native silica aerogels can be fabricated byderivatizing their surface with an organic moiety. This moiety makes theskeletal oxide structure flexible and able to withstand considerablestresses (see K. Kanamori, M. Aizawa, K. Nakanishi, T. Hanada, J.Sol-Gel Sci. Techn., 2008, 28, 172). In embodiments, surfactants arealso added to the gelation solution. These surfactants help control poresize distribution which, in turn, helps reducing freezing stresses (seeG. W. Scherer, “Freezing gels”, Journal of Non-Crystalline Solids 155(1993) 1-25).

In embodiments, a method for producing a native aerogel is provided, themethod comprising: (a) providing a first solution comprising analkoxide; (b) providing a second solution comprising a catalyst; (c)mixing the first and second solutions to provide a gelation mixture; (d)optionally pouring the solutions (or gelation mixture) into a mold;wherein the mixing of the first and second solutions results information of a wet gel as a result of hydrolysis of the alkoxide andpolymerization of the hydrolyzed alkoxide; and (e) after gelation,freeze-drying the wet gel to form an aerogel. Further, after gelationand before freeze-drying, solvent exchange may be applied to the gel toremove excess water. Also, embodiments may include addition of asurfactant to the first solution or the second solution or the gelationmixture.

In embodiments of the method, porous matrices are synthesized through amodification of hydrolysis condensation of alkoxides in which additionof water is reduced, or minimized. The reaction occurs in an organicsolvent and water with a concentration of water of approximately 4.4%v/v or lower, such as an ethanol-water azeotrope mixture (as used inthis specification, references to “ethanol” are intended to mean anethanol-water azeotrope mixture); the water in the azeotrope slowlyhydrolyzes the alkoxide. Lower water concentrations can also be employedbut they usually increase gelation time. In embodiments, water can bepresent in the gelation solution in an amount ranging from about 0.05%v/v to about 5% v/v, such as from 0.1% v/v to 4% v/v, or from about 0.2%v/v to 3% v/v, or from 0.3% v/v to 2% v/v, or from 0.4% v/v to 1.5% v/v,or from about 0.5% v/v to 1% v/v, or from about 0.6% v/v to 0.8% v/v.Water can also be provided by adding to the gelation solution hydratedmetal salts. Instead of water, a compound that reacts with the alkoxideor dissociates at high temperature and liberates water could be used,such as formic acid. In embodiments, any mixture of water and an organicsolvent can be used. For example, a mixture of acetone and water, oralcohol and water, or methanol and water, or butanol and water, orpropanol and water can be used. Additionally, after gelation, the porousmatrix (or aerogel) is freeze dried. Suitable freeze-drying techniquesare found in the art, including for example as disclosed by GermanPatent Application Publication No. DE10233703 A1 and correspondingGerman Patent No. DE10233703 B4.

For example, in one embodiment of the method, porous matrices aresynthesized by hydrolyzing an alkoxide without adding any water beyondthat present in the ethanol-water azeotrope. First tetramethylorthosilicate (TMOS) or polyethoxydisiloxane (PEDS) is dissolved intoethanol. Separately, a second solution is prepared which containsethanol and an amine such as triethanolamine. The two solutions are thenmixed and poured into a mold and a gel forms typically within about anhour. The gel is then removed from the mold and freeze dried to yield aporous material (aerogel). Alternatively, the gel can be freeze dried inthe mold. The ethanol used in the procedure may be an ethanol-watermixture which contains no more than 4-5% water by volume. Additionally,a base or acid is added during the hydrolysis step as a catalyst.Additional processing steps include a curing step performed overnight.

In embodiments, the first and second solutions are combined to provide agelation mixture or composition and the alkoxide is present in an amountranging from about 0.1% v/v to 50% v/v based on total volume of thecomposition, and/or the composition comprises an amine present in anamount ranging from about 0.1% v/v to 20% v/v based on total volume ofthe gelation mixture, and/or the composition comprises an organicsolvent present in an amount ranging from about 20% v/v to 90% v/v basedon total volume of the gelation mixture. In embodiments, the organicsolvent can be present in these concentrations and can be chosen fromone or more of an alcohol or a ketone, such as one or more of ethanol,methanol, butanol, propanol, acetone, or dimethylsulfoxide.

In one particular embodiment (described in detail in Example 1 below),water is used as a solvent in the composition in lieu of any organicsolvent. For example, in one embodiment, native silica aerogels areprepared by combining urea, cetyl trimethylammonium bromide (CTAB), andAcetic Acid with water as the solvent and thoroughly mixing thesereagents. Methyltrimethoxysilane is added to the solution to form agelation composition or mixture and continually stirred for 30 minutes.This composition is then poured into a mold and placed in an oven at 60t for 36 hours to allow for gelation and aging. Water is removed throughsolvent exchange with an organic solvent to prepare for thefreeze-drying step. Once solvent exchange is completed so the waterconcentration is less than 5% of the volume solvent, the monoliths arefrozen and then dried.

The gelation mixture or composition may comprise a ratio of alkoxide tosolvent (whether it is water, organic solvent, or a mixture of water andorganic solvent) at about 1:99 to 99:1, such as from 2:98 to 98:2, orfrom 3:97 to 97:3, or from 5:95 to 95:5, or from 10:90 to 90:10, or from20:80 to 80:10, or from 30:70 to 70:30, or from 40:60 to 60:40, or50:50, or any range within these ratio ranges. The gelation mixture maycomprise a ratio of catalyst to solvent at about 1:99 to 99:1, such asfrom 2:98 to 98:2, or from 3:97 to 97:3, or from 5:95 to 95:5, or from10:90 to 90:10, or from 20:80 to 80:10, or from 30:70 to 70:30, or from40:60 to 60:40, or 50:50, or any range within these ratio ranges.Likewise, the ratio of catalyst to alkoxide may be around 1:99 to 99:1,such as from 2:98 to 98:2, or from 3:97 to 97:3, or from 5:95 to 95:5,or from 10:90 to 90:10, or from 20:80 to 80:10, or from 30:70 to 70:30,or from 40:60 to 60:40, or 50:50, 1:2, 2:1, 1:3, 3:1, 1:4, 4:1, 1:5,5:1, 1:6, 6:1, 1:10 or 10:1 and so on, or any range within these ratioranges. Such ratios may be determined by weight or by volume.

Fabrication of Cross-Linked Aerogels

In other embodiments, the present invention provides a method ofsynthesizing cross-linked aerogels in a single step and in a single potwithout requiring any solvent exchange. In addition, embodiments of theinvention allow for fabrication of custom aerogel parts with largedimensions, as well as high volume fabrication of aerogels. The customaerogel parts may be used in a variety of thermal insulationapplications.

According to embodiments, cross-linked silica aerogels (mechanicallystrong aerogels) are prepared. Their mechanical strength arises bycross-linking the skeletal oxide particles with a polymer (see U.S. Pat.Nos. 8,277,676 and 8,227,363). The strength of these materials allowsthem to withstand the freezing stresses. These gels may be fabricatedusing the inventors' previously reported methods (see InternationalPatent Application Publication No. WO 2016019308) with or without anyadditional modifications.

In embodiments, a method for producing a cross-linked aerogel isprovided, comprising a) mixing a first solution comprising an alkoxidewith a second solution comprising a catalyst, an acrylic monomer, asilica derivatizer and a polymerization initiator and optionally pouringthe solutions into a mold, wherein such mixing step results in theformation of a wet gel as a result of hydrolysis of the alkoxide andpolymerization of the hydrolyzed alkoxide, b) exposing the wet gel to astimulus with sufficient intensity to catalyze cross-linking of the wetgel by the polymerization initiator, and c) freeze-drying thecross-linked wet gel to form an aerogel.

In particular, the present invention in embodiments provides a method inwhich a porous monolith is synthesized, made mechanically robust bypolymer cross-linking and dried by freeze-drying into an aerogel,without requiring any intermediate processing steps and/or solventexchange.

Another specific embodiment of the method provides for the synthesis ofaerogel composites. A first solution is prepared by adding an alkoxidecarrying a polymerizable moiety (such as vinyltrimethoxysilane (VMOS))to a solution of ethanol and TMOS. A second solution is preparedseparately which contains ethanol, triethanolamine, a polymerizationinitiator and a monomer such as methylacrylate. The solutions are thenmixed and a gel is synthesized by mixing the two solutions. The gel isthen dried by freeze-drying. In alternative embodiments, the gel may bepolymerized before the drying step through thermal initiation orphotopolymerization.

According to an exemplary embodiment, cross-linked aerogels arefabricated by combining an alkoxide carrying a polymerizable moiety,e.g. vinyltrimethoxysilane (VMOS) or tetramethylorthosilane (TMOS),added to a primary, secondary or tertiary alcohol. A second solution isprepared separately which includes the same or another alcohol, acatalyst such as triethanolamine, a monomer such as methylmethacrylate,a silica derivatizer such as trimethoxysilylpropyl methacrylate and apolymerization initiator. If dry solvents are employed, water can beadded to reach a concentration of no more than 4-5% by volume of thesolvent. The two solutions are then mixed and poured into a mold.Gelation occurs within one hour. Next, polymerization is initiatedthermally if a thermal initiator is employed, or by photopolymerizationwhen a photoinitiator is used. After polymerization, the monoliths arefreeze dried.

In embodiments, the first solution may comprise a ratio of alkoxide toalcohol at about 1:99 to 99:1, such as from 2:98 to 98:2, or from 3:97to 97:3, or from 5:95 to 95:5, or from 10:90 to 90:10, or from 20:80 to80:10, or from 30:70 to 70:30, or from 40:60 to 60:40, or 50:50, or anyrange within these ratio ranges. The second solution may comprise aratio of catalyst to alcohol at about 1:99 to 99:1, such as from 2:98 to98:2, or from 3:97 to 97:3, or from 5:95 to 95:5, or from 10:90 to90:10, or from 20:80 to 80:10, or from 30:70 to 70:30, or from 40:60 to60:40, or 50:50, or any range within these ratio ranges. The secondsolution may comprise a ratio of monomer to alcohol of 1:99 to 99:1,such as from 2:98 to 98:2, or from 3:97 to 97:3, or from 5:95 to 95:5,or from 10:90 to 90:10, or from 20:80 to 80:10, or from 30:70 to 70:30,or from 40:60 to 60:40, or 50:50, or any range within these ratioranges. Likewise, the ratio of catalyst to alkoxide may be around 1:99to 99:1, such as from 2:98 to 98:2, or from 3:97 to 97:3, or from 5:95to 95:5, or from 10:90 to 90:10, or from 20:80 to 80:10, or from 30:70to 70:30, or from 40:60 to 60:40, or 50:50, 1:2, 2:1, 1:3, 3:1, 1:4,4:1, 1:5, 5:1, 1:6, 6:1, 1:10 or 10:1 and so on, or any range withinthese ratio ranges. Such ratios may be determined by weight or byvolume.

Freeze-Drying

In embodiments, the native silica and cross-linked aerogel monoliths canbe frozen by any freezing technique known in the art. If the gels arekept inside the original molds, freezing can be carried out by placingthe gels into liquid nitrogen, into a cryogenic mixture (e.g., dry-iceacetone bath), or inside a refrigerator. Any freezing method works,provided that the gels are brought to a temperature below the freezingtemperature of the solvent used for the synthesis or solvent exchange.Use of tert-butanol as a solvent appears to be especially advantageous,since this solvent freezes just about at room temperature and thereforeit does not require to be cooled to low temperatures (a householdfreezer is sufficient). However, any solvent with a low freezingtemperature may work, such as for example ethanol, 1-butanol, dimethylsulfoxide, and carbon tetrachloride. The frozen gel is then dried usinga conventional freeze dryer or, more simply, placed in a vacuum chamberwhich is pumped by a conventional rotary pump. The part of the chamberhosting the sample must be kept at temperatures on the order of thefreezing temperature of the solvent.

Improved Transparency

Additional embodiments include any method of increasing the transparencyof an aerogel. The methods may increase transparency through anymechanism, such as altering pore size and pore size distribution,changing the size and/or shape of skeletal aggregates, removingsubstances such as water or other reagents, and the like. Inembodiments, these methods may include but not be limited to the use ofheat treatments, uniaxial compression, the use of polyurethane monomersfor cross-linking instead of acrylic monomers, the use of organosilanes,the use of surfactants and drying control chemical additives, oradjusting the reaction conditions such as increasing the temperatureduring polymerization, increasing the amount of catalyst, reducing theconcentration of monomer, or using polyfunctional monomers. Such methodsare described in more detail in Example 2 below. Embodiments of theinvention also include aerogels with improved transparency as measuredby the level of light transmission through a sample of the aerogel.

Reagents

In any embodiment of the invention, the surfactants may includequaternary ammonium salts such as cetrimonium bromide (CTAB),cetylpyridinium chloride (CPC), benzalkonium chloride (BAC),benzethonium chloride (BZT), dimethyldioctadecylammonium chloride,dioctadecyldimethylammonium bromide (DODAB), and the like. However, inother embodiments other surfactants can be used, including anionicsurfactants (e.g. sulfates, sulfonates, phosphates, and carboxylates),zwitterionic surfactants (e.g. betaines), non-ionic surfactants (e.g.polyethylene glycol, polypropylene glycol), and the like.

In any embodiment of the invention, the alkoxide may be a siliconalkoxide such as the organo-orthosilicates tetraethyl orthosilicate(TEOS), tetramethyl orthosilicate (TMOS), polyethoxydisiloxane (PEDS),methyltrimethoxysilane (MTMS), or vinyltrimethoxysilane (VMOS).Alkoxides of other transition metals, as well as chlorides, nitrates oracetylacetonates can also be employed. In embodiments, for example,sodium silicate and/or aluminum chloride could be used in particular.Although silica may be used, any metal oxide and sulfide can also oralternatively be used.

In any embodiment of the invention, the gelation reaction may becatalyzed by an acid (such as a metal salt) or base (such as an amine)or a catalyst containing fluoride. To minimize the amount of water addedto the solution, a metal salt may be added as an acid catalyst. In oneembodiment, aluminum chloride is used. In other embodiments, saltscontaining other acidic ions including Cr³⁺, Fe³⁺ Bi³⁺, Be²⁺, NH₄ ⁺ areused. In other embodiments, acids such as hydrochloric acid, sulfuricacid, and nitric acid are used. Base catalysts may include amines suchas triethanolamine, diethanolmethylamine, dimethylethlyamine, ordimethanolmethylamine or hydroxides such as ammonium hydroxide. Otherembodiments may use ammonium fluoride.

Additionally, embodiments may employ an acrylate or acrylated monomerfor the synthesis of cross-linked aerogels, and the cross-linkingreaction may be catalyzed by photopolymerization or thermalpolymerization. Examples of acrylated monomers include HDDA (hexanedioldiacrylate) and acrylated DPHA (dipentaerythritol hexaacrylate). Othernon-limiting examples of acrylates include methyl acrylate, ethylacrylate, 2-chloroethyl vinyl ether, 2-ethylhexyl acrylate, hydroxyethylmethacrylate, butyl acrylate, and butyl methacrylate.

Photopolymerization of cross-linked aerogels may be initiated byincluding a photoinitiator in one of the precursor solutions. Examplesof photoinitiators include Eosin Y, Nile Red, Alizarine Red S, andRhodamine B. Other examples of photoinitiators are known (see Fouassieret al, Dyes as Photoinitiators or Photosensitizers of PolymerizationReactions, Materials 2010, 3, 5130-5142). Polymerization can be alsoinduced thermally or by using thermal initiators.

Exemplary alcohols for use in the gelation precursor solutions ormixtures or in solvent exchange may include methanol, ethanol, butanol,tert-butanol, isopropyl alcohol, isobutanol, benzyl alcohol, and thelike, including any one or more solvent having a low entropy of fusion,such as cyclohexane or tert-butanol (t-butanol). The alcohols may be anyprimary, secondary, or tertiary alcohol capable of freeze-drying.Additional solvents may be ketones, such as acetone, or acetonitrile, ormixtures of alcohols and these solvents.

The following Examples will describe the above exemplary embodiments inmore detail. However, it should not be used to limit the scope of theinvention.

By way of background to the Examples, freeze-drying of wet gel has beenpreviously reported by other groups (see L. F. Su, L. Miao, S. Tanemura,G. Xu, Sci. Technol. Adv. Mat. 2012, 13, 035003; A. Pons, L. Casas, E.Estop, E. Molins, K. D. M. Harris, M. Xu, J. Non-Cryst. Solids, 2012,358, 461; S. R. Mukai, H. Nishihara, H. Tamon, Micropor. Mesopor. Mat.,2003, 63, 43; and E. Degn Egeberg, J. Engell, Journal de PhysiqueColloques, 1989, 50 (C4), p. C4-23-C4-28). However, it has only beenconfirmed as a process capable of yielding powders and not monoliths.This is for two reasons: Freezing must be rapid; otherwise large solventcrystals may grow inside the pores and induce cracks. Most importantly,considerable amounts of water (up to 10% by volume) are commonlyemployed in the synthesis of wet gels. Water expands when frozen andleads to a fractured silica backbone. For this reason, freeze-drying isgenerally considered a viable method only for the production of aerogelpowders.

For example, in one previous work, gels were synthesized directly usingtert-butanol as a solvent (see L. F. Su, L. Miao, S. Tanemura, G. Xu,Sci. Technol. Adv. Mat. 2012, 13, 035003). However, cracked gels werereported, presumably because a large amount of water was employed in thesynthesis. In other work (see A. Pons, L. Casas, E. Estop, E. Molins, K.D. M. Harris, M. Xu, J. Non-Cryst. Solids, 2012, 358, 461; E. DegnEgeberg, J. Engell, Journal de Physique Colloques, 1989, 50 (C4), p.C4-23-C4-28), the gelation solvent was exchanged with tert-butanol priorto freezing. Tert-butanol has several advantages over water, the mostrelevant being lack of expansion upon freezing. In both cases, largefragments and monoliths with a size of a few millimeters were reported.However, both works lamented the extreme fragility of the materials.This was also the inventors' experience. If native silica gels (preparedby hydrolysis-condensation of, say, trimethylorthosilicate) wereemployed, aerogels in monolithic form could be obtained. However, theseaerogels were extremely fragile and turned into dust even with carefuland slight manipulation. To reduce cracking of the monoliths duringfreeze-drying, the inventors produced wet gels with flexible reinforcedsilica skeletons. The modified backbone withstands the freezingstresses. The result was native and cross-linked aerogels in monolithicform. Disk-shaped samples with a diameter of up to 4 cm have beenproduced, having been limited by the maximum size allowed by theparticular vacuum chambers used. The materials can be handled with thesame precautions used for handling native silica aerogels. Ifmechanically solicited, they may crack, but they do not turn into dust.

Example 1

Native Silica.

Wet gels were prepared following a published method (see K. Kanamori, M.Aizawa, K. Nakanishi, T. Hanada, J. Sol-Gel Sci. Techn., 2008, 28, 172).For this, 0.88 g of urea, 0.1167 g of cetyl trimethylammonium bromide(CTAB), 0.019 ml of Acetic Acid and 2.842 ml of water as the solvent arethoroughly mixed. 1.672 ml of methyltrimethoxysilane is added to thesolution and continually stirred for 30 minutes. This mixture is thenpoured into a mold and placed in an oven at 60 t for 36 hours to allowfor gelation and aging. Wet gels synthesized in this way are notsuitable for freeze-drying. They contain a large amount of water, whichexpands during freezing and cracks the gels. Starting from this point,the inventors' procedure differs from the published one (see K.Kanamori, M. Aizawa, K. Nakanishi, T. Hanada, J. Sol-Gel Sci. Techn.,2008, 28, 172). Water is removed through solvent exchange with anorganic solvent to prepare for the freeze-drying step. Once solventexchange is completed so the water concentration is less than 5% of thevolume solvent, the monoliths are frozen. If the gels are kept insidethe original molds, freezing can be carried out by placing the gels intoliquid nitrogen, into a cryogenic mixture (e.g., dry-ice acetone bath),or inside a refrigerator. Any freezing method works, provided that thegels are brought to a temperature below the freezing temperature of thesolvent used for the synthesis. Use of tert-butanol as a solvent appearsto be especially advantageous, since this solvent freezes just about atroom temperature and therefore it does not require to be cooled to lowtemperatures (a household freezer is sufficient). The frozen gel is thendried using a conventional freeze dryer or, more simply, placed in avacuum chamber which is pumped by a conventional rotary pump. The partof the chamber hosting the sample must be kept at temperatures on theorder of the freezing temperature of the solvent. This fabricationmethod yields a porous material (aerogel) with a density of about 0.2g/cm³ and a surface area of up to 450 m²/g.

Cross-linked aerogels are fabricated as follows. 0.5 ml of an alkoxidecarrying a polymerizable moiety (see N. Leventis, C. Sotiriou-Leventis,G. Zhang, A.-M. M. Rawashdeh, Nano Lett., 2002, 2, 957; C. Wingfield, A.Baski, M. F. Bertino, N. Leventis, D. P. Mohite, H. Lu, Chem. Mater.,2009, 21, 2108; and C. Wingfield, L. Franzel, M. F. Bertino, N.Leventis, J. Mater. Chem. 2011, 21, 11737), e.g. vinyltrimethoxysilane(VMOS) or tetramethylorthosilane (TMOS), is added to a solution of 0.5ml of an alcohol such as ethanol, butanol or tert-butanol or otherprimary, secondary or tertiary alcohol. A second solution is preparedseparately which consists of 1.0 ml of the same or another alcohol, 40μl of triethanolamine, between 0.2 and 1.5 ml of a monomer such asmethylmethacrylate, between 0.05 and 0.3 ml of a silica derivatizer suchas trimethoxysilylpropyl methacrylate and a polymerization initiator. Ifdry solvents are employed, water is added to reach a concentration of nomore than 4% by volume of the solvent. The two solutions are then mixedand poured into a mold. Gelation occurs within one hour. Next,polymerization is initiated thermally if a thermal initiator isemployed, or by photopolymerization when a photoinitiator is used.Polymerization engages the organic moiety on the pore surfaces andcross-links the oxide particles making up the skeleton of the gel. Itdiffers from the inventors' previous work only for the drying method.After polymerization, the monoliths are frozen following the procedurereported for native silica aerogels. This fabrication method yields aporous material (aerogel) with a density of about 0.25 g/cm³ and asurface area of −100 m²/g and a modulus of 50 MPa. This same chemistrywas used in the inventors' previous disclosure (see International PatentApplication Publication No. WO 2016019308). One difference being thatgels are now freeze-dried and not supercritically-dried.

Custom Shapes.

The aerogels can be cast into molds of any arbitrary shape. Molds andaerogels can be placed into a freeze dryer. After drying, the aerogelscan be removed from the molds to yield aerogel components with customshape. Fabrication of aerogels with custom shapes was reported in theinventors' original patent application and published recently (seeInternational Patent Application Publication No. WO 2016019308 and L. S.White, D. R. Echard, M. F. Bertino, X. Gao, S. Donthula, N. Leventis, N.Shukla, J. Kośny, S. Saeed and K. Saoud, Transl. Mater. Res. 3 (2016)).This work differs from the previous one because it allows use of anymolding material. Because of the high temperatures, supercriticalsolvent drying does not allow plastic molds, and certain metal molds canreact with the hot solvents. Freeze-drying is a much more benignapproach which has virtually no limitations on the type of molds.

Example 2

FIGS. 1A-1D show results of methods employed according to thisdisclosure. Aerogel monoliths can be produced by freeze drying (FIG.1A), and transparency of the monoliths can be improved by refinement ofthe synthesis procedure (FIG. 1B), by heat treatment (FIG. 1C) and/or byuniaxial compression (FIG. 1D).

Fabricating aerogel monoliths with sizes suitable for standardizedthermal and mechanical testing (most common thermal test for insulationis ASTM C518), requires boards with a minimum size of 15 cm×15 cm×2.5cm. In particular, a dryer for processes such size samples should beused. Another consideration is avoiding or preventing cracking of themonoliths during freeze drying.

Cracking occurs because solvent freezing induces considerable stresseson the solid skeleton of porous materials. The stresses are caused bygrowth of large crystals inside pores and solvent diffusion betweenpores. Because of the larger surface-to-volume ratio, the solvent insmall pores freezes at a lower temperature than the solvent in largepores. These different freezing temperatures cause diffusion of solventfrom the small to the large pores during freezing (see Journal ofnon-crystalline solids 155, 1-25 (1993)). Solvent diffusion alsosupports growth of crystals inside the larger pores. These crystals tendto grow even after they become as large as the pores and inducecracking. Solvent depletion generates also capillary stresses andcracking inside the small pores. Thus, mechanical reinforcement may benecessary to fabricate some monoliths.

Reinforcement can be provided by polymer cross-linking, by increasingthe density of the gels (i.e., using an excess of silica precursor) orby adding fibers to the gelation solution (see Journal ofNon-Crystalline Solids 385 55-74 (2014)). All of these strategies arestraightforward to implement and yield materials which are at least oneorder of magnitude stronger than native aerogels. The critical size(i.e., the largest size that can be dried without fragmentation) dependson the bulk modulus of the material. Aerogels produced in the past byfreeze drying (see K. Kanamori, M. Aizawa, K. Nakanishi, T. Hanada,“Elastic organic-inorganic hybrid aerogels and xerogels”, J Sol-Gel SciTechnol (2008) 48, 172-181) had a modulus of about 1 MPa and a criticalsize of 3-5 mm. Reinforced aerogels have a modulus of up to 100 timesthe modulus of native aerogels (see Nano Lett. 2, 957-960 (2002)). Acritical size of between 30 and 50 cm is desirable. Additionally, somereinforcement techniques yield transparent materials. FIGS. 2A and 2Bcompares native and aerogels cross-linked with polyurethane, driedsupercritically. Polyurethane cross-linking yields smaller secondaryparticles than acrylic cross-linking (used in FIGS. 1A-1D), and,consequently, more transparent materials.

Strategies for reducing freezing stresses can also be used, which wouldeliminate or alleviate the need for reinforcement. One such strategy isto use solvents with a low entropy of fusion such as cyclohexane ortert-butanol (t-butanol). T-butanol was employed for the fabrication ofthe sample in FIG. 1A. However, it contained water and methanol assynthesis byproducts. These solvents are detrimental to freeze drying.Removal of these solvents by evaporation prior to gelation or by solventexchange after gelation yields aerogels with improved transparency (FIG.1B). Drying stresses can be further reduced by synthesizing gels with anarrow pore size distribution. Pore size distributions can be controlledby adding to the gelation solution an amphiphilic surfactant (seeMicropor. and Mesopor. Mater. 158, 247-252 (2012)) or a polar moleculethat binds to silanol groups such as dimethylformamide (see MicroporousMaterials 12, 63-69 (1997)). Narrow pore size distributions typicallygreatly aid freeze drying. The solvent in the pores will freeze at thesame temperature, solvent diffusion will be minimized and so thestresses.

Achieving higher transparency is also desired for some applications anduses. As shown in FIGS. 2A and 2B, transparent, mechanically strongmaterials can be produced by a careful selection of the cross-linkingpolymer using supercritical drying. The transparency of the materials inFIGS. 2A and 2B can be increased by reducing the concentration of thecrosslinker and by controlling pore size distribution (see Micropor. andMesopor. Mater. 158, 247-252 (2012); see Microporous Materials 12, 63-69(1997)). Achieving a sufficient transparency would eliminate the needfor densification and sandwiching, since the composites are mechanicallystrong. Transparency can also be improved by heating and/or by uniaxialcompression. Both strategies reduce the mean pore size, which is themain source of light scattering (see Microporous Materials 12, 63-69(1997)). In the case of cross-linked materials, heating also removes thepolymer and improves transparency, as shown in FIG. 1C. In embodiments,uniaxial compression is an alternative to heating to attain transparency(see Journal of Sol-Gel Science and Technology 14, 249-256 (1999)). InFIG. 1D the inventors show a monolith that had been reinforced with ahoneycomb polymer pattern (as part of another project) and compressed toabout 50% of the original thickness. Increasing density (ρ) hasadvantages and disadvantages. It increases the mechanical strength,which has a ρ^(3.1) dependence, but also the thermal conductivity, whichhas a ρ^(1.5) dependence. Preferred densification strategies aretargeted to achieve transparent materials with p˜0.15-0.17 g/cm³.Aerogels in this density range have been shown to exhibit excellenttransparency when heated at 800° C. (see Microporous Materials 12, 63-69(1997)). Assuming the starting aerogel having p˜0.1 g/cm³, minimummodulus of 1 MPa, and thermal conductivity of ˜15 mW/m-K, and using theabove power relationships, the resulting densified aerogel is expectedto have a minimum modulus of 6-8 MPa and thermal conductivity of 27-30mW/m-K.

Fabrication of i) transparent, ii) mechanically robust monoliths by iii)freeze drying can be achieved. Control of the skeletal nanostructure ofthe aerogels is one factor in producing such materials. Transparency andhaze are related to the size of the skeletal aggregates and of the poresin the skeleton of the materials. Roughly, minimizing light scatteringrequires minimization of the size of the skeletal aggregates, of thepores, and of the pore size distribution. Mechanical reinforcement viapolymer cross-linking, however, tends to increase the size of theaggregates. Reinforcing the materials while minimizing the size increaseof the skeletal nanoparticles is one way to address the issue.Particular strategies to improve transparency and maintain transparencyin freeze-dried, cross-linked aerogels are discussed below.

A. Controlling Morphology and Size of Pores and Aggregates.

The comparatively poor properties of aerogels are due, for the mostpart, to light scattering. The microscopic structure of aerogelsconsists of primary particles with a size <5 nm which aggregate intosecondary particles with a size of 20-30 nm. Correspondingly, there aretwo types of pores in aerogels. Micropores are the pores between primaryparticles and have a size <10 nm. Mesopores are the pores between thesecondary particles and have a size of tens of nanometers. Aconsiderable amount of theoretical and experimental work has shown thatlight scattering in aerogels depends on size and morphology of all thesestructures (particles and pores). (See P. B. Wagh, R. Begag, G. M.Pajonk, A. V. Rao, D. Haranatha, “Comparison of some physical propertiesof silica aerogel monoliths synthesized by different precursors”,Materials Chemistry and Physics 57 (1999) 214-218; A. Emmerling, R.Petricevic, A. Beck, P. Wang, H. Scheller, J. Fricke, “Relationshipbetween optical transparency and nanostructural features of silicaaerogels”, Journal of Non-Crystalline Solids 185 (1995) 240-248; E.Economopoulos, T. Ioannides, “Synthesis of transparent silica aerogelsusing tetraalkylammonium fluoride catalysts”, J Sol-Gel Sci Technol(2009) 49, 347-354; K. Kanamori, M. Aizawa, K. Nakanishi, and T. Hanada,“New Transparent Methylsilsesquioxane Aerogels and Xerogels withImproved Mechanical Properties”, Adv. Mater. 2007, 19, 1589-1593; and M.Nogami, S. Hotta, K. Kugimiya, H. Matsubara, “Synthesis andcharacterization of transparent silica-based aerogels usingmethyltrimethoxysilane precursor”, J Sol-Gel Sci Technol (2010) 56,107-113). However, literature reports are fragmented and sometimescontradictory. For example, Nogami et al. showed a strong correlationbetween transparency and mean pore size, while Economopoulos et al.reported a weak dependence on pore size. Another study showed thataerogels composed of fibril-like, fractal secondary aggregates are moretransparent than aerogels composed of globular aggregates (T. M.Tillotson and L. W. Hrubesh, “Transparent ultralow-density silicaaerogels prepared by a two-step sol-gel process”, Journal ofNon-Crystalline Solids 145 (1992) 44-50). However, another study reportsthe opposite, and attributes the difference to larger pore sizes andpore size distributions of fibrillar aggregates compared to globularaggregates (K. Kanamori, M. Aizawa, K. Nakanishi, and T. Hanada, “NewTransparent Methylsilsesquioxane Aerogels and Xerogels with ImprovedMechanical Properties”, Adv. Mater. 2007, 19, 1589-1593). The reason forthese apparently contradictory results is, likely, the large number ofparameters involved in aerogel synthesis. These include type ofprecursors, type of catalysis (base, acid, or two-step), concentrationof catalyst, synthesis temperature, addition of surfactants andpore-directing agents and drying conditions. Many groups have fabricatedaerogels with improved transparency, but each of them has worked on alimited subset of parameters. Since the interplay of the synthesisparameters is complicated, it is not surprising that the literaturereports are sometimes contradictory. In addition, modeling of lightscattering has been often based on simplified assumptions and models(e.g., Rayleigh scattering), which put considerable emphasis on the sizeof pores and skeletal nanostructure, but not on their shape. Thus,considerable experimental activity has focused on pore size control,while aggregate shape control has been less actively investigated (seeP. B. Wagh, R. Begag, G. M. Pajonk, A. V. Rao, D. Haranatha, “Comparisonof some physical properties of silica aerogel monoliths synthesized bydifferent precursors”, Materials Chemistry and Physics 57 (1999)214-218; and M. Nogami, S. Hotta, K. Kugimiya, H. Matsubara, “Synthesisand characterization of transparent silica-based aerogels usingmethyltrimethoxysilane precursor”, J Sol-Gel Sci Technol (2010) 56,107-113). More sophisticated simulation approaches, such as the discretedipole approximation (DDA) (often used to simulate light scattering fromaerosols, but generally not used for aerogels) (see T. Kozasa, J. Blum,T. Mukai, “Optical properties of dust aggregates I.”, Astron. Astrophys.263, 423-32 (1992); and T. Kozasa, J. Blum, T. Mukai, “Opticalproperties of dust aggregates II.”, Astron. Astrophys. 276, 278-88(1993)) show that the shape of aggregates plays a very important role.DDA results for aggregates of silica nanoparticles (10 nm radius) withdifferent fractal dimensions are reported in FIGS. 3A and 3B. Thesimulations show that globular aggregates (right) scatter light atlarger angles than aggregates with a lower fractal dimension (left).Thus, aerogels with a fibrillar nanostructure are likely to be less hazythan aerogels with a globular nanostructure, in agreement with resultsby the Hrubesch group (see T. M. Tillotson and L. W. Hrubesh,“Transparent ultralow-density silica aerogels prepared by a two-stepsol-gel process”, Journal of Non-Crystalline Solids 145 (1992) 44-50)and by the Nakanishi group (see K. Kanamori, M. Aizawa, K. Nakanishi,and T. Hanada, “New Transparent Methylsilsesquioxane Aerogels andXerogels with Improved Mechanical Properties”, Adv. Mater. 2007, 19,1589-1593). Controlling pore size and aggregate morphology appears to behelpful.

Comparing the transparency of aerogels with globular and fibrillarnanostructure is one way to increase understanding of the factorsinvolved in obtaining greater transparency. To obtain a globularnanostructure, wet gels can be synthesized by base catalysis oftetramethylorthosilicate (TMOS). To obtain a fractal, fibrillar-likenanostructure, a two-step catalysis (acid and then base) oftetraethylorthosilicate (TEOS) can be used (see T. M. Tillotson and L.W. Hrubesh, “Transparent ultralow-density silica aerogels prepared by atwo-step sol-gel process”, Journal of Non-Crystalline Solids 145 (1992)44-50). Based on the results presented in FIGS. 3A and 3B, gels obtainedby TEOS are expected to exhibit the lowest haziness. Given the manycontradictory literature reports, exploration of both morphologies iswarranted. In addition, TMOS is the most widely used precursor for thefabrication of transparent aerogels and its investigation can provide abaseline. The synthesis conditions will be varied to tune the size ofthe secondary particles. One important parameter appears to be catalystconcentration. Most available evidence (see A. Emmerling, R. Petricevic,A. Beck, P. Wang, H. Scheller, J. Fricke, “Relationship between opticaltransparency and nanostructural features of silica aerogels”, Journal ofNon-Crystalline Solids 185 (1995) 240-248; A. V. Rao, S. D. Bhagat,“Synthesis and physical properties of TEOS-based silica aerogelsprepared by two step (acid-base) sol-gel process”, Solid State Sciences6 (2004) 945-952; and E. Economopoulos, T. Ioannides, “Synthesis oftransparent silica aerogels using tetraalkylammonium fluoridecatalysts”, J Sol-Gel Sci Technol (2009) 49, 347-354) suggests that highcatalyst concentrations favor nucleation over growth, lead to smalleraggregates and increase transparency. A parameter that has been seldominvestigated is temperature. Gelation time is usually greatly reducedwhen the temperature is increased even by a few degrees (see S. Sakkaand H. Kozuka, Rheology of sols and fiber drawing”, Journal ofnon-crystalline solids, 100, 142-153 (1988)). Rapid gelation will likelyinhibit growth of secondary particles and help produce aerogels with thesmallest possible secondary aggregates.

Organosilanes may also play a role in obtaining greater transparency.Di- and tri-functional silicon alkoxides such as methyltrimethoxysilane(MTMS) and polyethoxydisiloxane (PEDS) have been shown in someinvestigations to lead to materials with increased transparency (see K.Kanamori, M. Aizawa, K. Nakanishi, T. Hanada, “Elastic organic-inorganichybrid aerogels and xerogels”, J Sol-Gel Sci Technol (2008) 48, 172-181;P. B. Wagh, R. Begag, G. M. Pajonk, A. V. Rao, D. Haranatha, “Comparisonof some physical properties of silica aerogel monoliths synthesized bydifferent precursors”, Materials Chemistry and Physics 57 (1999)214-218; A. V. Rao, S. D. Bhagat, “Synthesis and physical properties ofTEOS-based silica aerogels prepared by two step (acid-base) sol-gelprocess”, Solid State Sciences 6 (2004) 945-952; I. Adachi, T.Sumiyoshi, K. Hayashi, N. Iida, R. Enomoto, K. Tsukada, R. Suda, S.Matsumoto, K. Natori, M. Yokoyama, H. Yokogawa, “Study of a thresholdCherenkov counter based on silica aerogels with low refractive indices”,Nuclear Instruments and Methods in Physics Research A 355 (1995)390-398; K. Kanamori, M. Aizawa, K. Nakanishi, and T. Hanada, “NewTransparent Methylsilsesquioxane Aerogels and Xerogels with ImprovedMechanical Properties”, Adv. Mater. 2007, 19, 1589-1593; and A. Yu.Barnyakov, M. Yu. Barnyakov, V. V. Barutkin, V. S. Bobrovnikov, A. R.Buzykaev, A. F. Daniluk, S. A. Kononov, V. L. Kirillov, E. A.Kravchenko, A. P. Onuchin, “Influence of water on optical parameters ofaerogel”, Nuclear Instruments and Methods in Physics Research A 598(2009) 166-168). However, some authors have also reported thatorganosilanes degrade the optical properties of aerogels (see N. Husingand U. Schubert, “Organofunctional Silica Aerogels”, Journal of Sol-GelScience and Technology 8, 807-812 (1997); and N. Husing, U. Schubert, K.Misof and P. Fratzl, “Formation and Structure of Porous Gel Networksfrom Si(OMe)₄ in the Presence of A(CH2)nSi(OR)₃ (A) Functional Group”,Chem. Mater. 1998, 10, 3024-3032). There are several reasons for thisdiscrepancy. For example the transparency of aerogels synthesized usingTEOS, TMOS and PEDS was investigated (see A. V. Rao, S. D. Bhagat,“Synthesis and physical properties of TEOS-based silica aerogelsprepared by two step (acid-base) sol-gel process”, Solid State Sciences6 (2004) 945-952; and D. Lee, P. C. Stevens, S. Q. Zeng, A. J. Hunt,“Thermal characterization of carbon-opacified silica aerogels”, Journalof Non-Crystalline Solids 186 (1995) 285-290). The aerogels, however,were prepared using different water and catalyst concentrations for eachprecursor. PEDS aerogels had the highest catalyst concentration. Thehigh catalyst concentration may explain the higher transparency becauseof formation of smaller secondary particles. Thus, it is difficult tounderstand whether the higher transparency of PEDS was due to thecatalyst concentration or the precursor. More recent work (see K.Kanamori, M. Aizawa, K. Nakanishi, T. Hanada, “Elastic organic-inorganichybrid aerogels and xerogels”, J Sol-Gel Sci Technol (2008) 48, 172-181;and K. Kanamori, M. Aizawa, K. Nakanishi, and T. Hanada, “NewTransparent Methylsilsesquioxane Aerogels and Xerogels with ImprovedMechanical Properties”, Adv. Mater. 2007, 19, 1589-1593) has shown thathigh transparency can be attained using organosilanes when a surfactantis added to the gelation solution. The surfactant prevents phaseseparation induced by the hydrophobic organic moiety (methyl) attachedto the organosilane. Increased transparency by addition of surfactantsis in overall agreement with the trend of other authors such as Husing(see N. Husing and U. Schubert, “Organofunctional Silica Aerogels”,Journal of Sol-Gel Science and Technology 8, 807-812 (1997); N. Husing,U. Schubert, K. Misof and P. Fratzl, “Formation and Structure of PorousGel Networks from Si(OMe)4 in the Presence of A(CH2)nSi(OR)3 (A)Functional Group)”, Chem. Mater. 1998, 10, 3024-3032), wheretransparency was highest when organosilanes were employed which carriedhydrophilic moieties. Combination of surfactants and organosilanesappears the most promising strategy to limit the size of skeletalsecondary aggregates and improve transparency. Surfactants are astandard way of limiting nanoparticle growth, while the organic moietycarried by organosilanes inhibits condensation and helps prevent growthof secondary particles. (see P. B. Wagh, R. Begag, G. M. Pajonk, A. V.Rao, D. Haranatha, “Comparison of some physical properties of silicaaerogel monoliths synthesized by different precursors”, MaterialsChemistry and Physics 57 (1999) 214-218; I. Adachi, T. Sumiyoshi, K.Hayashi, N. Iida, R. Enomoto, K. Tsukada, R. Suda, S. Matsumoto, K.Natori, M. Yokoyama, H. Yokogawa, “Study of a threshold Cherenkovcounter based on silica aerogels with low refractive indices”, NuclearInstruments and Methods in Physics Research A 355 (1995) 390-398; I.Adachi, T. Sumiyoshi, K. Hayashi, N. Iida, R. Enomoto, K. Tsukada, R.Suda, S. Matsumoto, K. Natori, M. Yokoyama, H. Yokogawa, “Study of athreshold Cherenkov counter based on silica aerogels with low refractiveindices”, Nuclear Instruments and Methods in Physics Research A 355(1995) 390-398). Systematic investigation of organosilanes and extensionto alkoxides carrying vinyl-, acrylic- and styrene-groups is importantand necessary. These alkoxides have long chains that may further reduceparticle growth and increase hydrophobicity. The role played byorganosilanes should be clarified to attain optimal transparency, butalso because they are relevant to cross-linking and freeze drying.Cross-linking typically employs derivatization of the pores using anorganosilane carrying a polymerizable moiety. Organosilanes increase theflexibility of the aerogel skeleton (see K. Kanamori, M. Aizawa, K.Nakanishi, T. Hanada, “Elastic organic-inorganic hybrid aerogels andxerogels”, J Sol-Gel Sci Technol (2008) 48, 172-181; and K. Kanamori, M.Aizawa, K. Nakanishi, and T. Hanada, “New TransparentMethylsilsesquioxane Aerogels and Xerogels with Improved MechanicalProperties”, Adv. Mater. 2007, 19, 1589-1593), which is beneficial forfreeze drying. The derivatizing moiety can be introduced by exchangingthe gelation solvent with a solution of the desired trifunctionalalkoxide. However, processing steps could be saved by performingsynthesis and derivatization in the same step. Organosilane precursorscan also be used alone or in combination with TEOS, TMOS and otheralkoxides.

In addition to controlling the skeletal morphology and size, lighttransmission can be improved by precise control of pore size and poresize distribution. This can be achieved to a high degree by usingsurfactants and drying control chemical additives (DCCA). By varyingDCCA (e.g., glycerol) and/or surfactant concentration, materials withtunable pore sizes and extremely narrow pore size distributions can beobtained, which, in turn, have high transparency (see D. Haranath, A. V.Rao, and P. B. Wagh, “Influence of DCCAs on Optical Transmittance andPorosity Properties of TMOS Silica Aerogels”, Journal of PorousMaterials 6, 55-62 (1999); A. V. Rao, M. M. Kulkarni, “Effect ofglycerol additive on physical properties of hydrophobic silicaaerogels”, Materials Chemistry and Physics 77 (2002) 819-825; K.Kanamori, M. Aizawa, K. Nakanishi, and T. Hanada, “New TransparentMethylsilsesquioxane Aerogels and Xerogels with Improved MechanicalProperties”, Adv. Mater. 2007, 19, 1589-1593; and M. Nogami, S. Hotta,K. Kugimiya, H. Matsubara, “Synthesis and characterization oftransparent silica-based aerogels using methyltrimethoxysilaneprecursor”, J Sol-Gel Sci Technol (2010) 56, 107-113). Narrow pore sizedistributions also help the freeze drying effort by leading to uniformfreezing temperatures throughout the monolith and minimizing solventdiffusion and mechanical stresses, as discussed below in Section C.

Samples can be characterized with optical methods, but also and withscanning electron microscopy (SEM) and small-angle X-ray scattering(SAXS) (two alternative and complementary methods for structuralinvestigation of the nanostructure of aerogels), and solid-state nuclearmagnetic resonance (NMR) spectroscopy.

B. Transparent Cross-Linked Aerogels.

For cross-linked aerogels, transparency has been seldom reported, andthis is related to the cross-linking polymer and to the polymerizationkinetics. As shown in FIG. 4, the cross-linking polymer attaches to thesurface of the primary particles and yields a conformal coating of theoxide skeleton. It reinforces the aerogels but it also increases thesize (and thus the scattering) of the skeletal aggregates. Thus,cross-linked aerogels are typically opaque.

FIGS. 2A, 2B, and 5, however, show that adequate choice of cross-linker(polyurethane) and processing conditions (high temperatures) yieldstransparent materials. A key for transparency is increasing the rate ofthe polymerization reaction to reduce the size of the polymeraggregates. Increased polymerization rates can be readily achieved withurethanes. To cross-link with urethanes, the gelation solution istypically exchanged with a solution of acetone and an isocyanate. Thegel is then heated to about 60° C. (in a closed vessel to preventsolvent evaporation) to initiate polymerization (see M. A. B. Meador, L.A. Capadona, L. McCorkle, D. S. Papadopoulos, and N. Leventis,“Structure-Property Relationships in Porous 3D Nanostructures as aFunction of Preparation Conditions: Isocyanate Cross-Linked SilicaAerogels”, Chem. Mater. 2007, 19, 2247-2260). The polymerizationtemperature is determined by the low boiling temperature of the solvent(acetone). When a solvent with a higher boiling point (e.g., propylenecarbonate) is used, one can work at higher temperatures. Highertemperatures accelerate the polymerization reaction and limit the sizeof polymer aggregates. For example, the transparent samples shown inFIGS. 2A, 2B, and 5 were synthesized at 100° C. Likely, highertemperatures could further improve transparency.

Transparency could be further increased in two ways. Reducing theconcentration of monomer in the gelation solution appears to be safestand most immediate solution. The sample with best transparency (secondleft, top panel, FIG. 5) had also the lowest concentration ofcross-linker. Yet, its mechanical properties were quite reasonable: themodulus was ˜15 MPa and the stress at break was ˜1 MPa (see N. Leventis,C. Sotiriou-Leventis, G. Zhang, and A.-M. M. Rawashdeh Nano Letters,2002, 2 (9), 957-960; M. A. B. Meador, L. A. Capadona, L. McCorkle, D.S. Papadopoulos, and N. Leventis, “Structure-Property Relationships inPorous 3D Nanostructures as a Function of Preparation Conditions:Isocyanate Cross-Linked Silica Aerogels”, Chem. Mater. 2007, 19,2247-2260; G. Zhang, A. Dass, A.-M. M. Rawashdeh, J. Thomas, J. A.Counsil, C. Sotiriou-Leventis, E. F. Fabrizio, F. Ilhan, P. Vassilaras,D. A. Scheiman, L. McCorkle, A. Palczer, J. C. Johnston, M. A. Meador,N. Leventis, “Isocyanate-crosslinked silica aerogel monoliths:preparation and characterization”, Journal of Non-Crystalline Solids 350(2004) 152-164; and L. S. White, M. F. Bertino, S. Saeed, K. Saoud,“Influence of silica derivatizer and monomer functionality andconcentration on the mechanical properties of rapid synthesiscross-linked aerogels”, Microporous and Mesoporous Materials, 217,244-252 (2015)). An alternative way of decreasing monomer concentrationis use of polyfunctional monomers (e.g., di-isocyanates andtri-isocyanates). In recent work, the present inventors showed thatpolyfunctional cross-linkers yielded materials with high modulus even atlow concentration. The reason is probably formation of highlycross-linked, rigid polymer networks (see L. S. White, M. F. Bertino, S.Saeed, K. Saoud, “Influence of silica derivatizer and monomerfunctionality and concentration on the mechanical properties of rapidsynthesis cross-linked aerogels”, Microporous and Mesoporous Materials,217, 244-252 (2015)).

Another way of increasing transparency is to use materials with afibrillar instead of a globular skeletal structure. As the inventorsshow in FIGS. 6A and 6B, the cross-linking polymer builds a conformalcoating of the oxide structure. If the starting structure is fibrillaras in FIG. 6A, the coating increases the diameter of the fibrils but itdoes not bridge between them. However, if the starting structure is moreglobular (FIG. 6B), the polymer can bridge between adjacent branches.The result provides an aggregate which is larger than the startingstructure, and scattering is increased. The native and the cross-linkedsamples reported in FIGS. 2A, 2B, and 5 can further be optimized fortransparency, where light transmission was of about 65% in the sample ofFIGS. 2A and 2B (which was optimized for strength, contained about 50%of polymer by weight and had a modulus of about 100 MPa), and of about75% in the sample of FIG. 5 (which had a modulus of 15 MPa).

C. Fabrication of Transparent Aerogels/Monoliths by Freeze Drying.

The results reported in FIGS. 1A-1D show that aerogel monoliths can beproduced by freeze drying. The fabrication of monoliths is typicallylimited by the size of the freeze dryer. Fabrication of aerogel paneswith a minimum size of 15×15 cm and a thickness of up to 25 mm arepossible with appropriately sized freeze dryers. This size is theminimum necessary to measure thermal conductivity with ASTM C518, whichis the most common thermal test for insulation. Aerogels according tothe invention can be prepared with thicknesses ranging from 1 mm to 50mm, for example, such as from 2-40 mm, or from 3-30 mm, or from 4-25 mm,or from 5-45 mm, or from 8-20 mm, such as from 15-28 mm, or from 18-32mm, or from 9-24 mm, or from 12-26 mm, and so on. Up-sizing to tens ofcm needs to address stresses within the solid skeleton of porousmaterials induced by the freezing process. The stresses are caused bygrowth of large crystals inside pores and solvent diffusion betweenpores. Because of the larger surface-to-volume ratio, the solvent insmall pores freezes at a lower temperature than the solvent in largepores. These different freezing temperatures cause diffusion of solventfrom the small to the large pores during freezing (see G. W. Scherer,“Freezing gels”, Journal of Non-Crystalline Solids 155 (1993) 1-25).Solvent depletion generates capillary stresses and cracking inside thesmall pores. Solvent diffusion also supports growth of crystals insidethe large pores. These crystals tend to grow even after they become aslarge as the pores and induce cracking. To minimize freezing stresses,solvents with a low entropy of fusion can be employed, such ascyclohexane and tert-butanol (t-butanol). For example, t-butanol wasemployed for the fabrication of the sample in FIG. 1A. Cross-linking hasbeen realized as one way to strengthen the aerogels and preventfragmentation. This indicates that considerable stresses arise withinthe monolith, even though t-butanol is being employed. Cross-linkinglikely allows up-scalable fabrication of monoliths. The critical partsize (i.e., the largest size that can be dried without fragmentation)that can be fabricated by freeze drying depends on the modulus of thematerial. Aerogels produced in the past by freeze drying (see E. DegnEgeberg, J. Engell, “Freeze drying of silica gels prepared fromsiliciumethoxid”, Journal de Physique Colloques, 1989, 50 (C4), p.C4-23-C4-28) had a modulus <0.1 MPa and a critical part size of 3-5 mm,see also FIG. 7. Cross-linked aerogels have a modulus of up to 100 timesthe modulus of native aerogels (see N. Leventis, C. Sotiriou-Leventis,G. Zhang, and A.-M. M. Rawashdeh Nano Letters, 2002, 2 (9), pp 957-960).Materials having a critical part size of between 30 and 50 cm can beproduced using the methods described herein.

In addition to cross-linking, strategies to reduce stresses and increasetransparency should also be considered. One is refining the syntheticprocedure. The sample of FIG. 2A the gelation solution containedsynthesis byproducts, such as water and methanol. These solvents aredetrimental to freeze drying (see E. Degn Egeberg, J. Engell, “Freezedrying of silica gels prepared from siliciumethoxid”, Journal dePhysique Colloques, 1989, 50 (C4), p. C4-23-C4-28). Removal of thesesolvents by solvent exchange after gelation yields aerogels withimproved light transmission (FIG. 2B). Solvent exchange is not expectedto represent a processing bottleneck, since window panes are thin (<¼inch), thus solvent exchanges can be completed in a few hours.

A second strategy is use of urethane cross-linkers instead of theacrylics used in FIGS. 1A-1D. As shown in FIGS. 2A and 2B, urethane is across-linker that yields the strongest, yet transparent materials.Acrylics tend to yield opaque materials with a lower modulus thanurethane cross-linkers (see L. S. White, M. F. Bertino, S. Saeed, K.Saoud, “Influence of silica derivatizer and monomer functionality andconcentration on the mechanical properties of rapid synthesiscross-linked aerogels”, Microporous and Mesoporous Materials, 217,244-252 (2015)). An additional way of reducing freezing stresses is tosynthesize materials with a narrow pore size distribution. Because ofthe narrow pore size distribution, the solvent in the pores will freezeat nearly the same temperature, solvent diffusion will be minimized andso will the stresses. The efforts to improve transparency by narrowingpore size distribution described above in Section A can also greatly aidfreeze drying. Early work to fabricate translucent monoliths by freezedrying has been performed (see E. Degn Egeberg, J. Engell, “Freezedrying of silica gels prepared from siliciumethoxid”, Journal dePhysique Colloques, 1989, 50 (C4), p. C4-23-C4-28). In this work,translucent aerogels granules (7-8 mm in size) were obtained by using aDCCA to control pore size distribution, see FIG. 7. The gels were agedfor a long time (>7 days) to strengthen their structure, and wereexchanged several times with t-butanol to remove by-products andsolvents from the original gelation solution. In more recent work (seeL. F. Su, L. Miao, S. Tanemura and G. Xu, “Low-cost and fast synthesisof nanoporous silica cryogels for thermal insulation applications”, Sci.Technol. Adv. Mater. 13 (2012) 035003; and A. Pons, L. Casas, E. Estop,E. Molins, K. D. M. Harris, M. Xu, “A new route to aerogels: Monolithicsilica cryogels”, Journal of Non-Crystalline Solids 358 (2012) 461-469)opaque granules and monoliths were obtained, likely because of use oft-butanol containing some moisture. In the study by Egeberg, (see E.Degn Egeberg, J. Engell, “Freeze drying of silica gels prepared fromsiliciumethoxid”, Journal de Physique Colloques, 1989, 50 (C4), p.C4-23-C4-28), provides that t-butanol must be dry, or else it expandswhen frozen. Solvent expansion enlarges and cracks pores, increasingscattering.

Yet another alternative strategy can minimize freezing stresses and thisis synthesis of flexible monoliths. Flexible aerogels can be produced bycareful tuning of density and concentration of cross-linking agent (seeL. A. Capadona, M. A. B. Meador, A. Alunni, E. F. Fabrizio, P.Vassilaras, N. Leventis, “Flexible, low-density polymer crosslinkedsilica aerogels”, Polymer 47 (2006) 5754-5761), by using a flexiblecross-linker (see H. Guo, B. N. Nguyen, L. S. McCorkle, B. Shonkwilerand M. A. B. Meador, “Elastic low density aerogels derived frombis[3-(triethoxysilyl)propyl]disulfide, tetramethylorthosilicate andvinyltrimethoxysilane via a two-step process”, J. Mater. Chem., 2009,19, 9054-9062), or by coating the oxide surfaces with methyl groupswhich repel each other and prevent compression-induced sintering ofoxide nanoparticles (see K. Kanamori, M. Aizawa, K. Nakanishi, T.Hanada, “Elastic organic-inorganic hybrid aerogels and xerogels”, JSol-Gel Sci Technol (2008) 48, 172-181; K. Kanamori, M. Aizawa, K.Nakanishi, and T. Hanada, “New Transparent Methylsilsesquioxane Aerogelsand Xerogels with Improved Mechanical Properties”, Adv. Mater. 2007, 19,1589-1593 A. V. Rao, S. D. Bhagat, H. Hirashima, G. M. Pajonk,“Synthesis of flexible silica aerogels using methyltrimethoxysilane(MTMS) precursor”, Journal of Colloid and Interface Science (2006) 300,279-285). Flexible aerogels can be synthesized which are highlytransparent (see K. Kanamori, M. Aizawa, K. Nakanishi, T. Hanada,“Elastic organic-inorganic hybrid aerogels and xerogels”, J Sol-Gel SciTechnol (2008) 48, 172-181; K. Kanamori, M. Aizawa, K. Nakanishi, and T.Hanada, “New Transparent Methylsilsesquioxane Aerogels and Xerogels withImproved Mechanical Properties”, Adv. Mater. 2007, 19, 1589-1593) andcan recover from a linear strain as large as 80%, as shown in FIGS.8A-8C. Flexible aerogels are promising for freeze drying, since theirflexible structure could accommodate freezing stresses. Preliminaryresults, reported in FIG. 8C), show that flexible aerogels can be freezedried without the need for mechanical reinforcement. The dried aerogelwas opaque, likely because of residual water. The synthetic procedurereported previously (see K. Kanamori, M. Aizawa, K. Nakanishi, T.Hanada, “Elastic organic-inorganic hybrid aerogels and xerogels”, JSol-Gel Sci Technol (2008) 48, 172-181) uses a high water concentration(50% by volume) in the gelation solution. Repeated washings witht-butanol are necessary to remove the water. The test sample of FIG. 8Cwas washed twice in a 10× excess t-butanol, which was likely notsufficient to remove all the water. T-butanol expanded during freezingand yielded an opaque material. More experimentation is being carriedout to determine the pore size distribution of the wet and dry gels andto determine the optimum number of washings.

There is an additional alternative to improve transparency, and this isheat treatment. Heat treatment reduces the mean pore size and pore sizedistribution and leads to transparent monoliths. For example, the groupsof Rao and Pajonk found that transparency of native aerogels increasesby heating to about 400° C., and then decreases with increasingtemperature (see P. B. Wagh, G. M. Pajonk, D. Haranath, A. V. Rao,“Influence of temperature on the physical properties of citric acidcatalyzed TEOS silica aerogels”, Materials Chemistry and Physics 50(1997) 76-81). Transparency increases again when the sinteringtemperature of aerogels is reached (˜1000° C.). The increase intransparency for mild heat treatment (<400° C.) is explained bydesorption of synthesis leftovers (see A. Yu. Barnyakov, M. Yu.Barnyakov, V. V. Barutkin, V. S. Bobrovnikov, A. R. Buzykaev, A. F.Daniluk, S. A. Kononov, V. L. Kirillov, E. A. Kravchenko, A. P. Onuchin,“Influence of water on optical parameters of aerogel”, NuclearInstruments and Methods in Physics Research A 598 (2009) 166-168), butalso by a mild narrowing of the pore size distribution. This result isin agreement with more recent work. Aerogels processed at 450° C., forexample, were used in one of the most successful aerogel window projectsfunded by the European Union (see K. I. Jensen, F. H. Kristiansen and J.M. Schultz, Public Final Report, Contract Number ENK6-CT-2002-00648,“Highly insulating and light transmitting aerogel glazing for superinsulating windows”, November 2005). When aerogels are processed attemperatures >400° C., sineresis occurs, which leads to larger pores andhigher scattering. Transparency is recovered only at temperatures closeto the sintering temperature, when the aerogel completely loses itsporosity. In the inventors' case, mild heat treatment could also be usedto remove (partially or totally) the cross-linking polymer, and thusfurther increase transparency, as shown in FIG. 1C).

Optimum thermal conductivity is also important to minimize thickness,costs and light scattering. Hydrophobicity is important to preventmoisture penetration, and ultraviolet resistance must be ensured toprevent degradation of the materials. All these properties can betweaked as appropriate.

Thermal conductivity is usually between 15 and 20 mW/m-K for nativeaerogels, around 30 mW/m-K for aerogels with a polymer content <20% byweight, and of about 50 mW/m-K for aerogels with a polymer content >50%by weight (see L. S. White, D. R. Echard, M. F. Bertino, X. Gao, S.Donthula, N. Leventis, N. Shukla, J. Kośny, S. Saeed and K. Saoud,“Fabrication of native silica, cross-linked, and hybrid aerogelmonoliths with customized geometries”, Transl. Mater. Res. 3 (2016); andN. Leventis, “Three-Dimensional Core-Shell Superstructures: MechanicallyStrong Aerogels”, Acc. Chem. Res., 2007, 40, pp 874-884). Thecalculations shown in FIG. 9 show that the U-values and compositethicknesses can be attained with a thermal conductivity of 30 mw/m-K(20% by weight max. of cross-linker, see also FIG. 5). Thermalconductivity could be lowered by another ˜20% by opacification (see J.Fricke, X. Lu, P. Wang, D. Buttner and U. Heinemann, “Optimization ofmonolithic silica aerogel insulants”, J. Heat Mass Transfer. 35,2305-2309 (1992); D. Lee, P. C. Stevens, S. Q. Zeng, A. J. Hunt,“Thermal characterization of carbon-opacified silica aerogels”, Journalof Non-Crystalline Solids 186 (1995) 285-290; T.-Y. Wei, S.-Y. Lu, andY.-C. Chang, “A New Class of Opacified Monolithic Aerogels of UltralowHigh-Temperature Thermal Conductivities”, J. Phys. Chem. C 2009, 113,7424-7428). For example, opacification can be carried out using TiO₂(see J. Wang, J. Kuhn, X. Lu, “Monolithic silica aerogel insulationdoped with TiO₂ powder and ceramic fibers”, Journal of Non-CrystallineSolids 186 (1995) 296-300), which is transparent. For TiO₂opacification, pre-synthesized nanoparticles can be added to thegelation solution, or a Ti alkoxide can be added directly to thegelation solution or via solvent exchange. The amount of opacifier canbe kept around 5% by weight to prevent phase separation, a commonoccurrence especially when nanoparticles are added to the solution (seeJ. Fricke, X. Lu, P. Wang, D. Buttner and U. Heinemann, “Optimization ofmonolithic silica aerogel insulants”, J. Heat Mass Transfer. 35,2305-2309 (1992); J. Kuhn, T. Gleissner, M. C. Arduini-Schuster, S.Korder, J. Fricke, “Integration of mineral powders into SiO₂ aerogels).A preferred thermal conductivity is 30 mW/m-K without opacification, and˜25 mW/m-K with opacification.

Hydrophobicity. As discussed in this Example, the most promisingfabrication pathway for the inventive composites is use ofmethyltrimethoxysilane (MTMS) as a precursor, surfactants to preventphase separation and for pore size control, and cross-linking usingisocyanates. This combination of precursors and cross-linkers can impartmechanical strength (from the cross-linker), flexibility (because of thederivatization of the nanoparticles with an organic group), and alsohydrophobicity (via the methyl group of MTMS). If other alternativesprove more feasible or yield better results, hydrophobicity could beintroduced by exchanging the gelation solution with a solution of MTMS,or by adding a hydrophobic monomer to the cross-linking isocyanate. Forexample, one could prepare a cross-linking solution of di-isocyanate, ofa multifunctional isocyanate carrying an acrylic moiety, and of a highlyhydrophobic monomer such as 2,3,4,5-pentafluorostyerene. All thesemonomers are commercially available and commonly used in industry, andthey have been used in the past to fabricate hydrophobic aerogels (seeU. F. Ilhan, E. F. Fabrizio, L. McCorkle, D. A. Scheiman, A. Dass, A.Palczer, M. A. B. Meador, J. C. Johnston and N. Leventis, “Hydrophobicmonolithic aerogels by nanocasting polystyrene on amine-modifiedsilica”, J. Mater. Chem., 2006, 16, 3046-3054).

Aging. Materials can be subjected to cycles of elevated temperature,moisture and UV radiation to test for aging. Among these parameters, itis expected that UV exposure will be the most critical. Silica,cross-linkers and hydrophobic derivatizers are not strongly affected byhigh temperatures. Moisture is likely not an issue, as long as thematerials remain hydrophobic. UV light, instead, can degrade the organiccomponents of the materials. To prevent UV degradation, the mostpractical way appears to be addition of a TiO² coating. TiO² istransparent in the visible, is a good UV absorber and it would alsocontribute to opacification. Composites can be analyzed with standardanalytical techniques (absorption spectroscopy, FT-IR, NMR, SEM, etc.)during the aging testing to determine the causes of deterioration andtweak the synthesis correspondingly.

D. Integration of Aerogel Panes into Products.

Panel produced by using the inventive techniques are likely goodcandidates for both Category 1 and Category 2 products. For a Category 1product a U-value <0.5 BTU/sf/hr/° F., a light transmittance >70% and athickness of <⅛ inch are required. In embodiments, the aerogels can havea light transmittance ranging from 10% up to 100%, such as from 15% to90%, or from 20% to 95%, or from 25% to 80%, or from 30% to 85%, or from40% to 75%, or from 60% to 78%, or from 70% to 98%, and so on. Thesimulations reported in FIG. 9 show that the required U-value can beattained by an aerogel pane with a thickness of 3/32 inch and a thermalconductivity of 30 mW/m-K. The required thermal conductivity is wellwithin the range of those of cross-linked aerogels, so it is expectedthat such panels can also have the required U-value with a thicknessbelow ⅛ inch. As for light transmittance, typical light transmittancereported in the literature for optimized aerogels is of 80% for astandard sample thickness of 10 mm (0.394 inch) (see K. Kanamori, M.Aizawa, K. Nakanishi, T. Hanada, “Elastic organic-inorganic hybridaerogels and xerogels”, J Sol-Gel Sci Technol (2008) 48, 172-181; and K.Kanamori, M. Aizawa, K. Nakanishi, and T. Hanada, “New TransparentMethylsilsesquioxane Aerogels and Xerogels with Improved MechanicalProperties”, Adv. Mater. 2007, 19, 1589-1593). Category 1 products,however, require panes ⅛ inch thick. The reduced thickness relaxes therequirements on light transmission. Using Beer-Lambert's law, a sample10 mm thick with a transmittance of 30% will have a transmittance of 80%when thinned down to ⅛ inch (approx. 3.55 mm). This transmittance of 30%(at 10 mm thickness) was achieved by the cross-linked samples of FIG. 5,which were not optimized for optical transparency. Thus, it appears thatcross-linked aerogels can be used as Category 1 products with minimaloptimization. These materials are mechanically strong (10-100 MPa inmodulus), can be glued without shearing (see L. S. White, D. R. Echard,M. F. Bertino, X. Gao, S. Donthula, N. Leventis, N. Shukla, J. Kośny, S.Saeed and K. Saoud, “Fabrication of native silica, cross-linked, andhybrid aerogel monoliths with customized geometries”, Transl. Mater.Res. 3 (2016)) and would only need a polycarbonate sheet ( 1/32 inchthick) on the exterior surface for scratch protection and a low-ecoating (0.1) to improve thermal insulation.

For a Category 2 product, a U-value of <0.40 BTU/sf/hr/° F., a lighttransmittance >80% and a thickness <¼ inch are required. The requiredU-value would require a minimum pane thickness of 5/32 inch for athermal conductivity of 30 mW/m-K, see FIG. 9. Using Beer-Lambert's law,a light transmittance of 80% for a 5/32 inch thick panel is equivalentto a light transmittance of 57% for a pane thickness of 10 mm. Thislight transmittance is easily achieved by aerogels. The panes would besandwiched between glass panes, 3/64 inch thick to increase mechanicalstrength. This configuration is particularly attractive for mechanicallyweak aerogels. The sandwich structure would require use of temperedglass to make composite as strong as a conventional glass pane. Temperedglass, in fact, has an ultimate strength ˜8 times higher than that ofsoda lime glass. For integration with Category 1 and 2 products,techniques to minimize scattering and reflection at the interfacesshould be employed, including determining optimum adhesives, andoptimizing low-e coatings. Seal edge and desiccant technology is also aconsideration to be integrated to fabricate a full-scale pane laminate.

Example 3

Translucent and transparent aerogels can also be fabricated fromcompositions disclosed by the Group of N. Leventis in Chem. Mater. 2006,18, 285-296. In brief, gels can be fabricated using3-aminopropyltriethoxysilane (APTES) and tetramethylorthosilicate assilica precursors. It is believed that APTES serves as derivatizer forthe pore walls and a catalyst for the gelation reaction.

Samples can be prepared for example using 0.350 ml TMOS, 0.067 ml APTES,0.626 ml Acetonitrile, and 0.105 ml H₂O. After gelation, the sample canbe placed in a leak-tight container filled with excess acetonitrile at a5:1 ratio and set in an oven for four hours at 70° C. The acetonitrilecan then be exchanged for fresh acetonitrile at a 5:1 ratio, and thenagain after 3 hours. The solvent can then be exchanged with a solutionof an isocyanate (such as di-isocyanate or tri-isocyanate) inacetonitrile. A typical solution comprises 0.560 g di-isocyanate in 10ml acetonitrile, however, other proportions are also possible. After anexchange for 24 hours, the sample can be placed in a 5:1 excessacetonitrile and placed in an oven at 70° C. for 24 hours. During thistime, the sample is cross-linked with di-isocyanate. After cross-linkingwith di-isocyanate is complete, the pore-filling acetonitrile solutioncan be exchanged with tert-butanol or another freeze-dryable solvent.The samples are typically exchanged with a 5:1 wash of tert-butanolthree times, with the first exchange taking two hours and the remainingwashes three hours. Besides t-butanol, typical solvents used in freezedrying are cyclohexane or dimethylsulfoxide (DMSO). These solvents arepopular because they freeze near room temperature. Other solvents suchas ethanol can be theoretically employed. However, most organic solventsrequire freezing to very low temperatures, which makes their use moreimpractical. It is preferred that the solvent used for freeze drying bekept “dry” (as free of water as possible (such as <1% by volume orbetter)). However, use of solvents that form a eutectic or a glassyphase with water, such as for example DMSO, could be potentiallyemployed.

Samples exhibiting a preferred level of transparency or translucency canbe obtained according to this procedure, which allows for very rapidgelation. Rapid gelation minimizes the size of light-scatteringaggregates and improves transparency. Rapid gelation can also beattained by gelation at high temperatures, and/or by using excesses ofacid or base catalysts, and/or by using di-isocyanates. Anotherpreferred technique includes aging the sample for a minimum of fourhours before cross-linking in an oven kept at 70° C., which is believedto reinforce the skeleton of the aerogel to withstand freezing stresses.Additionally, it has been found that samples that are frozen slowly havelower transparency than samples frozen quickly (for example, by usinghigher freezing temperatures). Higher transparency samples are possiblewhen freezing is performed in a manner to avoid the solvent from forminglarge crystals. Similarly, large samples tend to present a transparentouter layer and a translucent or opaque core, due to differences infreezing velocity at the surface and core. Samples can be frozen byplacing them in refrigerators, but are best refrigerated by placing theminto a pre-cooled liquid, such as water-antifreeze mixtures, or organicsolvents such as methanol. The higher density of the liquid (compared toair in a freezer) ensures more rapid cooling. Best results are obtainedwhen the temperature of the whole sample is brought below the freezingpoint of the sample in less than 4 minutes, but other velocities arepossible.

Using the preferred techniques, transparent aerogels result, as shown inFIGS. 10A-B. A transparent sample with a thickness of 6 mm is shown inFIG. 10A. A translucent 3 mm disk prepared without an oven aging step isshown in FIG. 10B. The samples have a density of 0.457 grams per cubiccentimeter, a surface area of about 350 m²/g and a mean pore radius of 5nm. For comparison, more opaque (but still translucent) aerogelsprepared according to other methods can result in samples having adensity of 0.457 grams per cubic centimeter, a surface area between 200and 250 m²/g, and a mean pore size of about 5 nm, with the lower surfacearea indicative of formation of light-scattering macropores in theopaque materials.

Adsorption isotherms for transparent and more cloudy materials are oftype IV, as shown in FIGS. 11A-B. In particular, pore size distributionsshown are calculated using the BJH approximation (FIG. 11A) and anadsorption isotherm of transparent and translucent regions of the samesample is shown (FIG. 11B), where the translucent region was in the coreand had been frozen more slowly than the outer regions. These resultsindicate that the materials were mostly mesoporous. Macropores intranslucent samples were not prevalent, but must have been present insufficient density to compromise the optical properties of thematerials.

The present invention has been described with reference to particularembodiments having various features. In light of the disclosure providedabove, it will be apparent to those skilled in the art that variousmodifications and variations can be made in the practice of the presentinvention without departing from the scope or spirit of the invention.One skilled in the art will recognize that the disclosed features may beused singularly, in any combination, or omitted based on therequirements and specifications of a given application or design. Whenan embodiment refers to “comprising” certain features, it is to beunderstood that the embodiments can alternatively “consist of” or“consist essentially of” any one or more of the features. Otherembodiments of the invention will be apparent to those skilled in theart from consideration of the specification and practice of theinvention.

It is noted in particular that where a range of values is provided inthis specification, each value between the upper and lower limits ofthat range is also specifically disclosed. The upper and lower limits ofthese smaller ranges may independently be included or excluded in therange as well. The singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. It is intendedthat the specification and examples be considered as exemplary in natureand that variations that do not depart from the essence of the inventionfall within the scope of the invention. Further, all of the referencescited in this disclosure are each individually incorporated by referenceherein in their entireties and as such are intended to provide anefficient way of supplementing the enabling disclosure of this inventionas well as provide background detailing the level of ordinary skill inthe art.

1-64. (canceled)
 65. A method of producing a hybrid aerogel, comprising:forming an alcogel from a gelation solution comprising a siloxane,polymerizable monomers, and a polymerization initiator; activating thepolymerization initiator in a selected pattern in the alcogel to formpolymer in said selected pattern from the polymerizable monomers; anddrying the alcogel to produce a composite comprising a patterned polymerwith aerogel cores in openings of the patterned polymer.
 66. The methodof claim 65 wherein the selected pattern is a honeycomb pattern.
 67. Themethod of claim 66 wherein at least some of the aerogel cores are atleast 50% visible light transmission.
 68. The method of claim 66 whereinthe drying is performed by freeze-drying.
 69. The method of claim 66wherein the aerogel cores are comprised of silica aerogel.
 70. Themethod of claim 66 wherein said at least one acrylic monomer comprises amultifunctional acrylic monomer.
 71. The method of claim 66 wherein saidat least one acrylic monomer comprises two or more acrylic monomers. 72.The method of claim 66 wherein activating is performed by selectiveexposure to electromagnetic radiation.
 73. The method of claim 72wherein the electromagnetic radiation is or includes visible light. 74.The method of claim 72 wherein activating is performed by application ofheat.
 75. The method of claim 72 wherein the forming, activating anddrying steps are performed in the same vessel.
 76. The method of claim72 wherein the polymerizable monomers are acrylates.
 77. The method ofclaim 72 wherein the siloxane undergoes hydrolysis condensation.
 78. Ahybrid aerogel, comprising: a patterned polymer with a plurality ofopenings; aerogel in each of the plurality of openings in the patternedpolymer, wherein the patterned polymer and aerogel are coextensive atthe location of the patterned polymer with the patterned polymerconforming to the aerogel at the location of the patterned polymer. 79.The hybrid aerogel of claim 77 wherein the patterned polymer is in ahoneycomb pattern.
 80. The hybrid aerogel of claim 77 wherein at leastsome of the openings are at least 50% visible light transmission. 81.The hybrid aerogel of claim 77 wherein the polymer is a polyacrylate.82. The hybrid aerogel of claim 77 wherein the aerogel is a silicaaerogel.